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Design of a Nanometric AlTi Additive for MgB2-Based Reactive Hydride Composites with Superior Kinetic Properties

تصميم مادة مضافة AlTi نانومترية لمركبات الهيدريد التفاعلي القائمة على MgB2 مع خصائص حركية فائقة
Authors: Thi Thu Le; Claudio Pistidda; Julián Puszkiel; María Victoria Castro Riglos; Fahim Karimi; Jørgen Skibsted; SeyedHosein Payandeh; +11 Authors

Design of a Nanometric AlTi Additive for MgB2-Based Reactive Hydride Composites with Superior Kinetic Properties

Abstract

Los compuestos de hidruro de estado sólido son una opción prometedora para sistemas de almacenamiento de hidrógeno eficientes y seguros. El sistema compuesto de hidruro reactivo de litio 2LiBH4 + MgH2/2LiH + MgB2 (Li-RHC) ha sido ampliamente investigado debido a su alta capacidad teórica de almacenamiento de hidrógeno y baja entalpía de reacción calculada (11.5% en peso de H2 y 45.9 kJ/mol de H2). En este documento, se presenta una investigación exhaustiva sobre el efecto de la formación de aleaciones de nano-TiAl en las propiedades de almacenamiento de hidrógeno del Li-RHC. El aditivo 3TiCl3·AlCl3 se utiliza como precursor de nanopartículas. Para las temperaturas y presiones de hidrógeno investigadas, la adición de ~5% en peso de 3TiCl3·AlCl3 conduce a tiempos de hidrogenación/deshidrogenación de solo 30 min y una capacidad de almacenamiento de hidrógeno reversible de 9,5% en peso. El material que contiene 3TiCl3·AlCl3 posee propiedades superiores de almacenamiento de hidrógeno en términos de velocidades y una capacidad de hidrógeno estable durante varios ciclos de hidrogenación/deshidrogenación. Estas mejoras se atribuyen a una nanoestructura in situ y una fase hexagonal AlTi3 observada por microscopía electrónica de transmisión de alta resolución. Esta fase actúa de una manera doble, primero promoviendo la nucleación de MgB2 tras la deshidrogenación y segundo suprimiendo la formación de Li2B12H12 tras el ciclo de hidrogenación/deshidrogenación.

Les composés hydrurés à l'état solide sont une option prometteuse pour des systèmes de stockage d'hydrogène efficaces et sûrs. Le système composite d'hydrure réactif de lithium 2LiBH4 + MgH2/2LiH + MgB2 (Li-RHC) a été largement étudié en raison de sa capacité théorique élevée de stockage d'hydrogène et de sa faible enthalpie de réaction calculée (11,5 % en poids de H2 et 45,9 kJ/mol de H2). Dans cet article, une étude approfondie de l'effet de la formation des alliages nano-TiAl sur les propriétés de stockage de l'hydrogène du Li-RHC est présentée. L'additif 3TiCl3·AlCl3 est utilisé comme précurseur de nanoparticules. Pour les températures et les pressions d'hydrogène étudiées, l'addition d'environ5 % en poids de 3TiCl3·AlCl3 conduit à des temps d'hydrogénation/déshydrogénation de seulement 30 min et à une capacité de stockage d'hydrogène réversible de 9,5 % en poids. Le matériau contenant 3TiCl3 ·AlCl3 possède des propriétés supérieures de stockage de l'hydrogène en termes de vitesses et une capacité d'hydrogène stable pendant plusieurs cycles d'hydrogénation/déshydrogénation. Ces améliorations sont attribuées à une nanostructure in situ et à une phase hexagonale AlTi3 observée par microscopie électronique à transmission haute résolution. Cette phase agit de manière double, en favorisant d'abord la nucléation de MgB2 lors de la déshydrogénation et en supprimant ensuite la formation de Li2B12H12 lors du cycle d'hydrogénation/déshydrogénation.

Solid-state hydride compounds are a promising option for efficient and safe hydrogen-storage systems. Lithium reactive hydride composite system 2LiBH4 + MgH2/2LiH + MgB2 (Li-RHC) has been widely investigated owing to its high theoretical hydrogen-storage capacity and low calculated reaction enthalpy (11.5 wt % H2 and 45.9 kJ/mol H2). In this paper, a thorough investigation into the effect of the formation of nano-TiAl alloys on the hydrogen-storage properties of Li-RHC is presented. The additive 3TiCl3·AlCl3 is used as the nanoparticle precursor. For the investigated temperatures and hydrogen pressures, the addition of ∼5 wt % 3TiCl3·AlCl3 leads to hydrogenation/dehydrogenation times of only 30 min and a reversible hydrogen-storage capacity of 9.5 wt %. The material containing 3TiCl3·AlCl3 possesses superior hydrogen-storage properties in terms of rates and a stable hydrogen capacity during several hydrogenation/dehydrogenation cycles. These enhancements are attributed to an in situ nanostructure and a hexagonal AlTi3 phase observed by high-resolution transmission electron microscopy. This phase acts in a 2-fold manner, first promoting the nucleation of MgB2 upon dehydrogenation and second suppressing the formation of Li2B12H12 upon hydrogenation/dehydrogenation cycling.

تعد مركبات هيدريد الحالة الصلبة خيارًا واعدًا لأنظمة تخزين الهيدروجين الفعالة والآمنة. تم التحقيق على نطاق واسع في نظام مركب هيدريد الليثيوم التفاعلي 2LiBH4 + MgH2/2LiH + MgB2 (Li - RHC) نظرًا لقدرته العالية على تخزين الهيدروجين النظري وانخفاض محتوى التفاعل المحسوب (11.5 ٪ بالوزن من H2 و 45.9 كيلو جول/مول من H2). في هذه الورقة، يتم تقديم تحقيق شامل في تأثير تكوين سبائك النانو- TiAl على خصائص تخزين الهيدروجين في Li - RHC. يتم استخدام المادة المضافة 3TiCl3 · AlCl3 كسلائف للجسيمات النانوية. بالنسبة لدرجات الحرارة وضغوط الهيدروجين التي تم فحصها، تؤدي إضافة 5 ٪ بالوزن من 3TiCl3·AlCl3 إلى أوقات الهدرجة/نزع الهيدروجين التي تبلغ 30 دقيقة فقط وسعة تخزين هيدروجين قابلة للعكس تبلغ 9.5 ٪ بالوزن. تمتلك المادة التي تحتوي على 3TiCl3 · AlCl3 خصائص تخزين هيدروجين فائقة من حيث المعدلات وقدرة هيدروجين مستقرة خلال العديد من دورات الهدرجة/نزع الهيدروجين. وتعزى هذه التحسينات إلى بنية نانوية في الموقع ومرحلة AlTi3 سداسية لوحظت بواسطة المجهر الإلكتروني عالي الدقة للإرسال. تعمل هذه المرحلة بطريقة مزدوجة، حيث تعمل أولاً على تعزيز نواة MgB2 عند نزع الهيدروجين وثانيًا قمع تكوين Li2B12H12 عند دورة الهدرجة/نزع الهيدروجين.

Countries
Italy, Argentina
Keywords

Composite material, Li-RHC, Hydrogen Storage, MgB2, Materials Science, Metal Hydrides, FOS: Physical sciences, Quantum mechanics, catalysts, hydrogen storage, https://purl.org/becyt/ford/2.5, Materials Chemistry, Al-Ti ADDITIVE, https://purl.org/becyt/ford/2, MgB2‑Based Reactive Hydride Composites, Artificial Nitrogen Fixation, Hydride, Chemical Hydrogen Storage, Metal, Mg based materials, Physics, HYDROGEN STORAGE, AlTi Additive, Synthesis and Properties of Boron-based Materials, Reactive material, Condensed Matter Physics, Materials science, 620, KINETIC PROPERTIES, Kinetics, Physics and Astronomy, Superconductivity in Magnesium Diboride (MgB2), Materials and Methods for Hydrogen Storage, Physical Sciences, Metallurgy, solid state hydrogen storage, reactive hydride composites, Kinetic energy, Nanocatalysts, ddc: ddc:620.11

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selected citations
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This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
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popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
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